A method for modifying wind power solid waste fibers by polymerization

Abstract

The application discloses a wind power solid waste fiber polymerization modification method and relates to the technical field of concrete materials. The modified wind power solid waste fiber can be better used in concrete materials, and recycling of the material is better realized. Nano silicon dioxide is generated on the surface of the wind power solid waste fiber, the contact area of the glass fiber with alkali aggregate in an alkaline environment can be reduced, then the pretreated wind power solid waste fiber is modified by using a silane coupling agent KH570, carbon-carbon double bonds are introduced on the surface of the pretreated wind power solid waste fiber, finally, under the action of an initiator azobisisobutyronitrile, fluorocarbon resin is formed on the surface of the wind power solid waste, and the in-situ generated silicon dioxide and fluorocarbon resin can realize physical / chemical double protection of the wind power solid waste. When the wind power solid waste is used in concrete, the wind power solid waste can also be prevented from reacting with alkali aggregate in an alkaline environment through physical / chemical double protection, and the durability of the material is improved.

Description

TECHNICAL FIELD

[0001] The application relates to the technical field of concrete materials, and particularly relates to a wind power solid waste fiber polymerization modification method. BACKGROUND

[0002] Wind power blades are usually made of glass fiber or carbon fiber reinforced composite materials and adopt thermosetting resin (such as epoxy resin) as a matrix material, and have the advantages of high strength, light weight and corrosion resistance, but also lead to difficulty in degradation and recycling after being discarded; the wind power blades are large in size (the length can reach dozens of meters) and complex in material structure, and the traditional landfill or incineration method not only occupies land but also may pollute the environment. Since the thermosetting resin cannot be re-melted like plastic, mechanical recycling can only crush the blades into low-value fillers, which is poor in economy. Therefore, how to efficiently and environmentally treat the discarded blades becomes a key challenge for the sustainable development of the wind power industry, and with the rapid growth of the installed capacity of wind power, the blades installed in the early stage (usually with a service life of 20-25 years) have begun to be retired. These blades made of composite materials (glass fiber / carbon fiber + epoxy resin) are difficult to degrade naturally, and the existing technology generally crushes the discarded wind power blades into particles or powders, adds them into concrete to replace the aggregates in the concrete, or adds the powders into wood-plastic materials to replace part of the raw materials; however, the glass fiber in the discarded wind power blade fibers is easy to cause alkali aggregate reaction in an alkaline environment, affecting the durability of the material. SUMMARY

[0003] In order to solve the above technical problems, the application provides a wind power solid waste fiber polymerization modification method.

[0004] The object of the application can be achieved by the following technical solutions.

[0005] A wind power solid waste fiber polymerization modification method, comprising the following steps:

[0006] In step S1, 25% ammonia water by mass fraction is added into an 85% ethanol aqueous solution by volume fraction, uniform stirring is performed, tetraethyl orthosilicate is added, uniform stirring is performed, and after 6h of reaction, the wind power solid waste fiber treated by irradiation is added. After 30min of ultrasonic treatment, the wind power solid waste fiber is transferred to a reaction kettle, the temperature is increased to 120-130 DEG C, and the reaction is kept for 3h. After the reaction is completed, the wind power solid waste fiber is washed with anhydrous ethanol and deionized water three times, respectively, and is dried to obtain pretreated wind power solid waste fiber.

[0007] In step S1, the nano silicon dioxide is generated on the surface of the wind power solid waste fiber by an in-situ generation method, so that the contact area of the glass fiber with the alkali aggregate in an alkaline environment can be reduced.

[0008] Step S2, KH570 was added into 20% volume fraction of ethanol aqueous solution, stirred at a constant speed for 10 min, pretreated wind power solid waste fiber was added, stirred at a constant speed at room temperature for 30 min, and dried to obtain modified wind power solid waste fiber;

[0009] In step S2, the pretreated wind power solid waste fiber was modified by silane coupling agent KH570 to introduce carbon-carbon double bond on the surface of the pretreated wind power solid waste fiber.

[0010] Step S3, the reaction kettle was vacuumed and argon was introduced, vinyl acetate, ethylene glycol monoallyl ether, tetrafluoroethylene and modified wind power solid waste fiber were added, azobisisobutyronitrile and mixed solvent were added, the temperature was increased to 60-65 DEG C, and the reaction was kept for 10 h, and then modified wind power solid waste fiber was obtained.

[0011] In step S3, under the action of initiator azobisisobutyronitrile, vinyl acetate, ethylene glycol monoallyl ether, tetrafluoroethylene and carbon-carbon double bond on the modified wind power solid waste fiber were polymerized, and fluorocarbon resin was formed on the surface of the wind power solid waste, and the in-situ generated silicon dioxide and fluorocarbon resin could realize physical / chemical double protection of the wind power solid waste, and when used in concrete, the wind power solid waste could also be protected by physical / chemical double protection to prevent alkali aggregate reaction in the alkaline environment of the wind power solid waste, affecting the durability of the material.

[0012] Further, the irradiated wind power solid waste fiber in step S1 is a wind power solid waste fiber treated by 100 KGy.

[0013] Further, the amount ratio of ammonia water, ethanol aqueous solution, tetraethyl orthosilicate and irradiated wind power solid waste fiber in step S1 is 11.2-11.8 mL:100 mL:5-6 mL:5-6 g.

[0014] Further, the weight ratio of KH570, ethanol aqueous solution and pretreated wind power solid waste fiber in step S2 is 1-1.2:100:20-30.

[0015] Further, the amount ratio of vinyl acetate, ethylene glycol monoallyl ether, tetrafluoroethylene, modified wind power solid waste fiber, azobisisobutyronitrile and mixed solvent in step S3 is 10-20 g:5-10 g:10-20 g:40-50 g:1-1.2 g:50-80 mL.

[0016] Further, the mixed solvent in step S3 is dimethylbenzene and butyl acetate mixed in a volume ratio of 1:1.

[0017] Further, the wind power solid waste fiber in step S1 is prepared by the following steps:

[0018] The first step is to sequentially pass the waste wind power blade through crushing and screening to obtain a fiber crude product.

[0019] The second step is to heat the prepared fiber crude product to 500-600 DEG C in an oxygen-free environment for 4-6h to decompose the residual resin and prepare the wind power solid waste fiber.

[0020] The application has the following beneficial effects: the modification method of the wind power solid waste fiber is disclosed, so that the modified wind power solid waste fiber can be better used in concrete materials, and the recycling of the recycled materials is better realized. The modification method first generates nano-silicon dioxide on the surface of the wind power solid waste fiber through in-situ generation, which can reduce the contact area of the glass fiber with the alkali aggregate in an alkaline environment. Then, the pretreated wind power solid waste fiber is modified by the silane coupling agent KH570 to introduce a carbon-carbon double bond on the surface of the pretreated wind power solid waste fiber. Finally, under the action of the initiator azobisisobutyronitrile, vinyl acetate, ethylene glycol monoallyl ether, tetrafluoroethylene and the carbon-carbon double bond on the modified wind power solid waste fiber are polymerized, and then a fluorocarbon resin can be formed on the surface of the wind power solid waste. The in-situ generated silicon dioxide and fluorocarbon resin can realize physical / chemical double protection of the wind power solid waste. When used in concrete, the wind power solid waste can also be protected by physical / chemical double protection to prevent alkali aggregate reaction in an alkaline environment, which affects the durability of the material. DETAILED DESCRIPTION

[0021] The technical solutions in the embodiments of the application will be described below in a clear and complete manner. Obviously, the described embodiments are only part of the embodiments of the application, rather than all the embodiments. Based on the embodiments in the application, all other embodiments obtained by those skilled in the art without creative labor fall within the scope of protection of the application.

[0022] Embodiment 1: a wind power solid waste fiber polymerization modification method, comprising the following steps:

[0023] Step S1, add 25% ammonia water to 85% ethanol aqueous solution by volume fraction, uniformly stir and add tetraethyl orthosilicate, uniformly stir and react for 6h, then add the wind power solid waste fiber treated by irradiation, ultrasonic treatment for 30min, then transfer to a reaction kettle, heat to 120-130 DEG C, and keep the temperature for 3h. After the reaction is completed, wash with anhydrous ethanol and deionized water three times respectively, and dry to prepare pretreated wind power solid waste fiber. The amount ratio of ammonia water, ethanol aqueous solution, tetraethyl orthosilicate and wind power solid waste fiber treated by irradiation is 11.2mL:100mL:5mL:g;

[0024] The wind power solid waste fiber is prepared by the following steps:

[0025] The first step, the waste wind power blade is sequentially crushed and screened to obtain a fiber crude product;

[0026] The second step, the prepared fiber crude product is heated to 500 DEG C in an oxygen-free environment for 4 hours to decompose the residual resin, and a wind power solid waste fiber is prepared.

[0027] The irradiation-treated wind power solid waste fiber is a wind power solid waste fiber treated by 100 KGy.

[0028] Step S2, KH570 is added to a 20% ethanol aqueous solution, stirred at a uniform speed for 10 minutes, pretreated wind power solid waste fiber is added, stirred at a uniform speed at room temperature for 30 minutes, dried, and modified wind power solid waste fiber is prepared, the weight ratio of KH570, ethanol aqueous solution and pretreated wind power solid waste fiber is controlled to be 1:100:20;

[0029] Step S3, the reaction kettle is vacuumed and argon is introduced, vinyl acetate, ethylene glycol monoallyl ether, tetrafluoroethylene and modified wind power solid waste fiber are added, azobisisobutyronitrile and mixed solvent are added, the temperature is raised to 60 DEG C, and the reaction is kept for 10 hours, and the modified wind power solid waste fiber is prepared after the reaction is completed, the amount ratio of vinyl acetate, ethylene glycol monoallyl ether, tetrafluoroethylene, modified wind power solid waste fiber, azobisisobutyronitrile and mixed solvent is controlled to be 10g:5g:10g:40g:1g:50mL;

[0030] The mixed solvent in step S3 is dimethylbenzene and butyl acetate mixed in a volume ratio of 1:1.

[0031] Embodiment 2: a wind power solid waste fiber polymerization modification method, comprising the following steps:

[0032] Step S1, 25% ammonia water is added to 85% ethanol aqueous solution, stirred at a uniform speed, tetraethyl orthosilicate is added, ultrasonic treatment is carried out for 30 minutes, and then the reaction kettle is transferred, the temperature is raised to 120-130 DEG C, and the reaction is kept for 3 hours, after the reaction is completed, the pretreated wind power solid waste fiber is washed with anhydrous ethanol and deionized water three times respectively, and dried, the amount ratio of ammonia water, ethanol aqueous solution, tetraethyl orthosilicate and irradiation-treated wind power solid waste fiber is controlled to be 11.4mL:100mL:5.2mL:5.2g;

[0033] The wind power solid waste fiber is prepared by the following steps:

[0034] The first step, the waste wind power blade is sequentially crushed and screened to obtain a fiber crude product;

[0035] Second step, the prepared fiber crude product is heated to 550 DEG C under oxygen-free environment, and is kept for 4 hours to decompose residual resin, and a wind power solid waste fiber is prepared.

[0036] The irradiation-treated wind power solid waste fiber is a wind power solid waste fiber treated by 100 KGy.

[0037] Step S2, the KH570 is added into a 20% ethanol aqueous solution, stirred at a uniform speed for 10 minutes, the pretreated wind power solid waste fiber is added, stirred at a uniform speed at room temperature for 30 minutes, dried, and a modified wind power solid waste fiber is prepared, and the weight ratio of KH570, the ethanol aqueous solution and the pretreated wind power solid waste fiber is controlled to be 1.1:100:22;

[0038] Step S3, the reaction kettle is vacuumed and argon is introduced, vinyl acetate, ethylene glycol monoallyl ether, tetrafluoroethylene and the modified wind power solid waste fiber are added, azobisisobutyronitrile and a mixed solvent are added, heated to 60 DEG C, and kept for 10 hours of reaction, and a modified wind power solid waste fiber is prepared after the reaction is completed, and the amount ratio of the vinyl acetate, the ethylene glycol monoallyl ether, the tetrafluoroethylene, the modified wind power solid waste fiber, the azobisisobutyronitrile and the mixed solvent is controlled to be 15 g:8 g:15 g:45 g:1.1 g:60 mL;

[0039] The mixed solvent in step S3 is dimethylbenzene and butyl acetate mixed in a volume ratio of 1:1.

[0040] Embodiment 3: a wind power solid waste fiber polymerization modification method, comprising the following steps:

[0041] Step S1, 25% ammonia water is added into 85% ethanol aqueous solution, stirred at a uniform speed, tetraethyl orthosilicate is added, ultrasonic treatment is carried out for 30 minutes, and then the irradiation-treated wind power solid waste fiber is transferred into a reaction kettle, heated to 125 DEG C, kept for 3 hours of reaction, washed with anhydrous ethanol and deionized water respectively for three times after the reaction is completed, dried, and a pretreated wind power solid waste fiber is prepared, and the amount ratio of the ammonia water, the ethanol aqueous solution, the tetraethyl orthosilicate and the irradiation-treated wind power solid waste fiber is controlled to be 11.6 mL:100 mL:6 mL:5.5 g;

[0042] The wind power solid waste fiber is prepared by the following steps:

[0043] First step, the abandoned wind power blade is sequentially subjected to crushing and screening, and a fiber crude product is obtained;

[0044] Second step, the prepared fiber crude product is heated to 600 DEG C under oxygen-free environment, and is kept for 6 hours to decompose residual resin, and a wind power solid waste fiber is prepared.

[0045] The irradiation-treated wind power waste fiber is a wind power waste fiber treated at 100 KGy.

[0046] Step S2, add KH570 to 20% ethanol aqueous solution, stir at a uniform speed for 10 min, add pretreated wind power waste fiber, stir at a uniform speed at room temperature for 30 min, dry, and prepare modified wind power waste fiber, control the weight ratio of KH570, ethanol aqueous solution and pretreated wind power waste fiber to be 1.2:100:28;

[0047] Step S3, vacuumize the reaction kettle and introduce argon, add vinyl acetate, ethylene glycol monoallyl ether, tetrafluoroethylene and modified wind power waste fiber, add azobisisobutyronitrile and mixed solvent, heat to 65℃, and keep the temperature for 10 h, and then prepare modified wind power waste fiber, control the amount ratio of vinyl acetate, ethylene glycol monoallyl ether, tetrafluoroethylene, modified wind power waste fiber, azobisisobutyronitrile and mixed solvent to be 18 g:8 g:18 g:45 g:1.2 g:70 mL;

[0048] The mixed solvent in step S3 is dimethylbenzene and butyl acetate mixed at a volume ratio of 1:1.

[0049] Embodiment 4: a wind power waste fiber polymerization modification method, comprising the following steps:

[0050] Step S1, add 25% ammonia water to 85% ethanol aqueous solution, stir at a uniform speed, add tetraethyl orthosilicate, stir at a uniform speed, and then add irradiation-treated wind power waste fiber after 6 h of reaction, transfer to a reaction kettle after ultrasonic treatment for 30 min, heat to 130℃, keep the temperature for 3 h, wash with anhydrous ethanol and deionized water respectively for three times after the reaction, dry, and prepare pretreated wind power waste fiber, control the amount ratio of ammonia water, ethanol aqueous solution, tetraethyl orthosilicate and irradiation-treated wind power waste fiber to be 11.8 mL:100 mL:6 mL:6 g;

[0051] The wind power waste fiber is prepared by the following steps:

[0052] First step, the waste wind power blade is sequentially crushed and sieved to obtain a fiber crude product;

[0053] Second step, the prepared fiber crude product is heated to 600℃ in an oxygen-free environment, and the residual resin is decomposed for 6 h to prepare wind power waste fiber.

[0054] The irradiation-treated wind power waste fiber is a wind power waste fiber treated at 100 KGy.

[0055] Step S2, KH570 was added into 20% volume fraction of ethanol aqueous solution, stirred at a constant speed for 10 min, the pretreated wind power solid waste fiber was added, stirred at a constant speed at room temperature for 30 min, and dried to obtain the modified wind power solid waste fiber, wherein the weight ratio of KH570, ethanol aqueous solution and pretreated wind power solid waste fiber was controlled to be 1.2:100:30;

[0056] Step S3, the reaction kettle was vacuumized and argon was introduced, vinyl acetate, ethylene glycol monoallyl ether, tetrafluoroethylene and the modified wind power solid waste fiber were added, azobisisobutyronitrile and mixed solvent were added, the temperature was increased to 65 DEG C, and the reaction was kept for 10 h, and the modified wind power solid waste fiber was prepared after the reaction was completed, wherein the amount ratio of vinyl acetate, ethylene glycol monoallyl ether, tetrafluoroethylene, modified wind power solid waste fiber, azobisisobutyronitrile and mixed solvent was controlled to be 20 g:10 g:20 g:50 g:1.2 g:80 mL;

[0057] The mixed solvent in step S3 is xylene and butyl acetate mixed in a volume ratio of 1:1.

[0058] Comparative Example 1: Compared with Example 1, the wind power solid waste fiber was not modified, and the wind power solid waste fiber was prepared by the following steps:

[0059] First step, the waste wind power blade was sequentially crushed and sieved to obtain a fiber crude product;

[0060] Second step, the prepared fiber crude product was heated to 500 DEG C in an oxygen-free environment, and the residual resin was decomposed for 4 h to obtain the wind power solid waste fiber.

[0061] Alkaline solution: simulated cement pore solution: 1 mol / L NaOH + 0.2 mol / L KOH + saturated Ca(OH)2 solution (pH≈13.5);

[0062] The wind power solid waste fibers prepared in Examples 1-4 and Comparative Example 1 were weighed and recorded as W0, soaked in the alkaline solution at 60 DEG C for 7 d, 14 d and 28 d, the samples were taken out, washed with deionized water, dried and weighed, recorded as W1, and the weight loss rate was calculated, the results are shown in Table 1 below:

[0063]

[0064] Table 1

[0065] Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 7d 3％ 4％ 4％ 5％ 12％ 14d 8％ 10％ 11％ 12％ 28％ 28d 15％ 19％ 18％ 19％ 46％

[0066] From Table 1 above, it can be seen that the wind power solid waste fiber prepared in Examples 1-4 has more excellent corrosion resistance.

[0067] The above merely illustrates and describes the concept of the present application, and those skilled in the art can make various modifications or supplements to the described specific embodiments or adopt similar ways to replace, as long as the modifications or supplements do not deviate from the concept of the present application or exceed the scope defined by the present claims, and the modifications or supplements shall fall within the protection scope of the present application.

Claims

1. A method of wind power solid waste fiber polymer modification, characterized in that, Comprising the following steps: Step S1, add ammonia water with mass fraction of 25% into ethanol aqueous solution with volume fraction of 85%, stir at constant speed, and then add tetraethyl orthosilicate, stir at constant speed, and then add wind power solid waste fiber treated by irradiation after 6h reaction, transfer to a reaction kettle after ultrasonic treatment for 30min, heat to 120-130℃, and keep temperature for 3h, then wash with anhydrous ethanol and deionized water respectively for three times, dry, and then obtain pretreated wind power solid waste fiber; Step S2, add KH570 into ethanol aqueous solution with volume fraction of 20%, stir at constant speed for 10min, add pretreated wind power solid waste fiber, stir at constant speed at room temperature for 30min, and then dry to obtain modified wind power solid waste fiber; Step S3, vacuumize the reaction kettle, introduce argon, add vinyl acetate, ethylene glycol monoallyl ether, tetrafluoroethylene, and modified wind power solid waste fiber, add azobisisobutyronitrile and mixed solvent, heat to 60-65℃, and keep temperature for 10h, then obtain modified wind power solid waste fiber after reaction; The wind power solid waste fiber treated by irradiation in step S1 is wind power solid waste fiber treated by 100KGy; The amount ratio of ammonia water, ethanol aqueous solution, tetraethyl orthosilicate, and wind power solid waste fiber treated by irradiation in step S1 is 11.2-11.8mL:100mL:5-6mL:5-6g; The weight ratio of KH570, ethanol aqueous solution, and pretreated wind power solid waste fiber in step S2 is 1-1.2:100:20-30; The amount ratio of vinyl acetate, ethylene glycol monoallyl ether, tetrafluoroethylene, modified wind power solid waste fiber, azobisisobutyronitrile, and mixed solvent in step S3 is 10-20g:5-10g:10-20g:40-50g:1-1.2g:50-80mL.

2. The method of claim 1, wherein the method is characterized by: The mixed solvent in step S3 is dimethylbenzene and butyl acetate mixed according to the volume ratio of 1:

1.

3. The method of claim 1, wherein the method further comprises: The wind power solid waste fiber in step S1 is prepared by the following steps: First step, crush and screen the abandoned wind power blade in sequence to obtain fiber crude product; Second step, heat the obtained fiber crude product to 500-600℃ in an oxygen-free environment, and keep temperature for 4-6h to obtain wind power solid waste fiber.

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